Linear viscoelasticity amorphous polymers

Contents Chain Configuration in Amorphous Polymer Systems. Material Properties of Viscoelastic Liquids. Molecular Models in Polymer Rheology. Experimental Results on Linear Viscoelastic Behavior. Molecular Entan-lement Theories of Linear iscoelastic Behavior. Entanglement in Cross-linked Systems. Non-linear Viscoelastic-Properties. 

According to the more widely used Williams, Landel, and Ferry (WLF) equations, all linear, amorphous polymers have similar viscoelastic properties at Tg and at specific temperatures above Tg, such as Tg + 25 K, and the constants Ci and C2 related to holes or free volume, the following relationship holds ... 

Linear amorphous polymers can behave as either Hookian elastic (glassy) materials, or highly elastic (rubbery) substances or as viscous melts according to prevailing temperature and time scale of experiments. The different transitions as shown schematically in Figure 5.1 are manifestations of viscoelastic deformations, which are time dependent [1]. 

What about semi-crystalline polymers Their viscoelastic behavior is much more complex, because of the superposition of the behavior of the crystalline and amorphous domains. This superposition is not necessarily linear, and coupling of the responses can occur, particularly as the degree of crystallinity of a sample is increased and the amorphous domains become constrained by the crystalline domains. Because of this, the behavior of semi-crystalline polymers is much less uniform than their amorphous counterparts, displaying individual idiosyncrasies that often have to be described separately. 

Linear viscoelastic behavior is actually observed with polymers only in very restricted circumstances involving homogeneous, isotropic, amorphous specimens subjected to small strains at temperatures near or above Tg and under test conditions that are far removed from those in which the sample may be broken. Linear viscoelasticity theory is of limited use in predicting service behavior of polymeric articles, because such applications often involve large strains, anisotropic objects, fracture phenomena, and other effects which result in nonlinear behavior. The theory is nevertheless valuable as a reference frame for a wide range of applications, just as the thermodynamic equations for ideal solutions help organize the observed behavior of real solutions. 

Figure 2.24 Five regions of viscoelastic behavior for a linear, amorphous polymer I (a to b), II (b to c), III (c to d), IV (d to e), and V ( e to f). Also illustrated are effects of crystallinity (dotted line) and cross-linking (dashed line).

Draw a logB versus temperature plot for a linear, amorphous polymer and indicate the position and name the five regions of viscoelastic behavior. How is the curve changed if (a) the polymer is semicrystalline, (b) the polymer is cross-linked, and (c) the experiment is run faster ... 

In spite of the often large contribution of secondary filler aggregation effects, measurements of the time-temperature dependence of the linear viscoelastic functions of carbon filled rubbers can be treated by conventional methods applying to unfilled amorphous polymers. Thus time or frequency vs. temperature reductions based on the Williams-Landel-Ferry (WLF) equation (162) are generally successful, although usually some additional scatter in the data is observed with filled rubbers. The constants C and C2 in the WLF equation... 

It is certain that the relaxation behavior of filled rubbers at large strains involves numerous complications beyond the phenomena of linear viscoelasticity in unfilled amorphous polymers. Breakdown of filler structure, strain amplification, failure of the polymer-filler bond, scission of highly extended network chains and changes in network chain configuration probably all play important roles in certain ranges of time, strain rate, and temperature. A clear understanding of the interplay of these effects is not yet at hand. 

The accurate applicability of linear viscoelasticity is limited to certain restricted situations amorphous polymers, temperatures near or above the glass temperature, homogeneous, isotropic materials, small strains, and absence of mechanical failure phenomena. Thus, the theory of linear viscoelasticity is of limited direct applicability to the problems encounted in the fabrication and end use of polymeric materials (since most of these problems involve either large strains, crystalline polymers, amorphous polymers in a glass state failure phenomena, or some combination of these disqualifying features). Even so, linear viscoelasticity is a most important subject in polymer materials science—directly applicable in a minority of practical problems, but indirectly useful (as a point of reference) in a much wider range of problems. 

In spite of these complications, the viscoelastic response of an amorphous polymer to small stresses turns out to be a relatively simple subject because of two helpful features (1) the behavior is linear in the stress, which permits the application of the powerful superposition principle and (2) the behavior often follows a time-temperature equivalence principle, which permits the rapid viscoelastic response at high temperatures and the slow response at low temperatures to be condensed in a single master curve. 

Our discussion of the viscoelastic properties of polymers is restricted to the linear viscoelastic behavior of solid polymers. The term linear refers to the mechanical response in whieh the ratio of the overall stress to strain is a function of time only and is independent of the magnitudes of the stress or strain (i.e., independent of stress or strain history). At the onset we concede that linear viscoelastie behavior is observed with polymers only under limited conditions involving homogeneous, isotropie, amorphous samples under small strains and at temperatures close to or above the Tg. In addition, test conditions must preclude those that ean result in specimen rupture. Nevertheless, the theory of linear viseoelastieity, in spite of its limited use in predicting service performance of polymeric articles, provides a useful reference point for many applications. 

The four-parameter model provides a crude quahtative representation of the phenomena generally observed with viscoelastie materials instantaneous elastie strain, retarded elastic strain, viscous flow, instantaneous elastie reeovery, retarded elastie reeovery, and plastic deformation (permanent set). Also, the model parameters ean be assoeiated with various molecular mechanisms responsible for the viscoelastic behavior of linear amorphous polymers under creep conditions. The analogies to the moleeular mechanism can be made as follows. 

Linear viscoelasticity is valid only imder conditions where structural changes in the material do not induce strain-dependent modulus. This condition is fulfilled by amorphous polymers. On the other hand, the structural changes associated with the orientation of crystalline polymers and elastomers produce anisotropic mechanical properties. Such polymers, therefore, exhibit nonlinear viscoelastic behavior. 

Fortunately for linear amorphous polymers, modulus is a function of time and temperature only (not of load history). Modulus-time and modulus-temperature curves for these polymers have identieal shapes they show the same regions of viscoelastic behavior, and in each region the modulus values vary only within an order of magnitude. Thus, it is reasonable to assume from such similarity in behavior that time and temperature have an equivalent effect on modulus. Such indeed has been found to be the case. Viscoelastic properties of linear amorphous polymers show time-temperature equivalence. This constitutes the basis for the time-temperature superposition principle. The equivalence of time and temperature permits the extrapolation of short-term test data to several decades of time by carrying out experiments at different temperatures. 

The occurrence of significant crystallinity in a polymer sample is of considraable consequence to a materials scientist. The properties of the sample — the density, optical clarity, modulus, and general mechanical response — all change dramatically when crystallites are present, and the polymer is no longer subject to the rules of linear viscoelasticity, which apply to amorphous polymers as outlined in Chapter 13. Howcvct, a polymer sample is rarely completely crystalline, and the properties also depend on the amonnt of crystalline order. 

The mechanical properties are dependent on both the chemical and physical nature of the polymer and the environment in which it is used. For amorphous polymers, the principles of linear viscoelasticity apply, but these are no longer valid for a semicrystalline polymer. The mechanical response of a polymer is profoundly influenced by the degree of crystallinity in the sample. 

Next we note that there are two physieally different sources of temperature and pressure dependence of the elastic constants of polymers. One, in common with that exhibited by all inorganic crystals, arises from anharmonic effects in the interatomic or intermolecular interactions. The second is due to the temperature-assisted reversible shear and volumetric relaxations under stress that are particularly prominent in glassy polymers or in the amorphous components of semi-crystalline polymers. The latter are characterized by dynamic relaxation spectra incorporating specific features for different polymers that play a central role in their linear viscoelastic response, which we discuss in more detail in Chapter 5. 

Thermoplasts are linear or weakly branched polymers. Their application temperature lies below the melting temperature in the case of crystalline polymers and below the glass transition temperature in the case of amorphous polymers. They are converted to an easily deformable plastic state on heating above these characteristic temperatures. This plastic state can be termed liquid with respect to the molecular order, or viscoelastic with respect to the rheological behavior. On cooling below the characteristic temperatures,... 

Figure 11 Five regions of viscoelastic behavior for a linear, amorphous polymer.

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